Treatment of cellulosic textile fabrics with methylolated alkoxyalkyl carbamates

ABSTRACT

The invention relates to treatment of cellulosic textile fabrics with methylolated alkoxyalkyl carbamate finishing agents to impart improved wrinkle and shrink resistance thereto. The novel finishing agents are prepared by reaction of formaldehyde with an alkoxyalkyl carbamate such as methoxyethyl carbamate. Methylolated alkyl carbamates and methylolated hydroxyalkyl carbamates have been employed for this same purpose in the past, but the methylolated alkoxyalkyl carbamates of the present invention provide treated fabrics which exhibit superior properties.

United States Patent Goodman, Jr. et a1.

[ TREATMENT OF CELLULOSIC TEXTILE FABRICS WITH METHYLOLATED ALKOXYALKYL CARBAMATES Inventors: Henry G. Goodman, Jr., White Plains; Carol A. Dupraz, Flushing (Corona); George H. Lourigan, New City, all of NY.

Union Carbide Corporation, New York, NY.

Filed: Feb. 16, 1966 Appl. No.: 527,772

Assignee:

US. Cl 8/187, 8/1 15.7, 260/482 C Int. Cl. D06m 13/40, D06m 15/54 Field of Search 8/116.3, 187; 260/482 C References Cited UNITED STATES PATENTS Shelly a a1. 8/1163 x Mar. 18, 1975 3,391,181 7/1968 Scheuer1....., 260/482 3,524,876 8/1970 Gregson 8/116.3X

Primary Examiner-George F. Lesmes Assistant Examiner-.l. Cannon Attorney, Agent, or F irm-Francis M. Fazio [57] ABSTRACT The invention relates to treatment of cellulosic textile fabrics with methylolated alkoxyalkyl carbamate fin-' 4 Claims, No Drawings TREATMENT OF CELLULOSIC TEXTILE FABRICS WITH METI-IYLOLATED ALKOXYALKYL CARBAMATES This invention relates to the preparation of textile fabrics having improved wrinkle and shrink resistance and other improved properties. More specifically, this invention relates to a process for treating cellulosic textile fabrics with methylolated alkoxyalkyl carbamates and to the treated fabrics produced thereby.

One of the important recent developments in the finishing of cellulosic textile fabrics has been the introduction of finishing agents prepared by reacting aliphatic monocarbamates with formaldehyde. These products have been found to be very effective in imparting wrinkle resistance and washwear properties to the fabric, while displaying the important advantages, as compared with conventional nitrogenous finishing agents, of enhanced resistance to chlorine damage and durability under conditions promoting acid hydolysis. Heretofore, finishing agents of this type have been prepared from alkyl carbamates, such as methyl, ethyl, propyl or butyl carbamate, or from hydroxyalkyl carbamates, such as hydroxyethyl carbamate, and have been observed from certain deficiencies, for example, with regard to abrasion resistance, tear strength and fabric hand, which have hindered their optimum commercial development. Moreover, these finishing agents, though greatly superior to conventional nitrogenous finishing agents such as dimethylol ethyleneurea or methylated methylolmelamine with respect to resistance to chlorine damage and durability to acid hydrolysis, are, in certain instances, still somewhat deficient in this regard. It is toward the objectives of overcoming these deficiencies and of providing treated textile fabrics of improved properties that the present invention is directed.

This invention is based on the discovery that finishing agents for treating cellulosic textile fabrics which are prepared by reaction of formaldehyde with an alkoxyalkly carbamate, as hereinafter define, permit the preparation of fabrics with superior properties as compared to the finishes derived from alkyl or hydroxyalkyl carbamates in accordance with the teachings of the prior art. It was unexpected and surprising to find that the methylolated alkoxyalkyl carbamates described herein are superior finishing agents to both the methylolated alkyl carbamates and methylolated hydroxylakyl carbamates. While applicants do not intend to be bound by any theoretical considerations, it is believed that this superior performance is predicated, to a degree, on the superior lubricating properties of the methylolated alkoxyalkyl carbamates, since fiber lubridity is an important factor in determining many fabric properties.

The alkoxyalkyl carbamates employed in preparing the textile treating agents of this invention are compounds of the general formula:

a value of from I to ID, and preferably of from l to 3. They may be prepared by any of several methods known to the art. A particularly convenient method of preparation involves the reaction of urea with a glycol ether of the formula:

where R, R and n are as defined above, to form the alkoxyalkyl carbamate and liberate ammonia. Illustrative of the glycol ethers within the scope of this definition are the methyl, ethy, butyl, isobutyl, hexyl and 2- ethylhexyl ethers of ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, polyethylene glycol, polypropylene glycol, and mixed polyethylene-polypropylene glycol.

The alkoxyalkyl carbamates described above are reacted with formaldehyde to produce the methylolated alkoxyalkyl carbamates having utility as textile finishing agents in accordance with this invention. The exact structure of the reaction product of formaldehyde with the alkoxyalkyl carbamate has not been established, but it is believed that a mixture of monomethylol and dimethylol derivatives results, viz., a mixture of an N- methylol alkoxyalkyl carbamate of the formula:

- a o-(R o) c u ca m;

and an N,N-dimethylol alkoxyalkyl carbamate of the formula:

- the formaldehyde is believed to be present as free formaldehyde and some as combined formaldehyde which is present in a form which has not yet been established.

Although the conditions under which the methylolation reaction is effected significantly affect-the performance characteristics of the reaction product, the reaction conditions are not narrowly critical. A suitable procedure is to dissolve the alkoxyalkyl carbamate in water, add the formaldehyde to the aqueous solution, adjust the pH to the desired level, and then heat the mixture for the period necessary to effect methylolation. Upon cooling, neutralization, dilution with water, and filtration, the product is recovered as a clear, colorless solution of the methylolated alkoxyalkyl carbamate.

The reaction of formaldehyde and the alkoxyalkyl carbamate may be effected at temperatures from about 20C., preferably about 50C., to the reflux temperature of the reaction mixture, i.e., slightly above I00C. Reaction times of from about If) minutes to about 24 hours, and preferably from about I to 5 hours, may be employed. The initial pH of the reaction mixture should be from about 4 to about 10, and preferably from about 8 to about 10.

The most important factor in determining the performance of the finishing agents is the ratio of formaldehyde to alkoxyalkyl carbamate employed. The reaction products of particular utility for the purposes of this invention are those prepared by reacting the formaldehyde with the alkoxyalkly carbamate in a molar ratio of from about 1.5 to about 3 moles of formaldehyde per mole of alkoxyalkyl carbamate, and preferably in a molar ratio of from about 2 to about 2.5.

Textile fabrics which are amenable to treatment with the finishing agents of this invention are the cellulosic textile fabrics. The term cellulosic textile fabric," as used throughout the specification and in the appended claims, is intended to include fabrics, whether woven or knitted, and garments or other articles made from such fabrics, and is also intended to include both cellulose fabrics, including regenerated cellulose, and cellulosecontaining fabrics. The cellulosic textile fabrics comprehended thus include cotton fabrics, linen fabrics, rayon fabrics, fabrics consisting of blends of cotton, linen or rayon fibers, and fabrics consisting of blends of cellulose fibers and non-cellulosic fibers.

The finish may be applied to the cellulosic textile fabric in any suitable manner known to the art, for example, by dipping or padding. Ordinarily, the finishing agent, which term is employed herein to mean the reaction product of formaldehyde and the alkoxyalkyl carbamate, is applied to the fabric from aqueous solution. Such aqueous treating solution may, if desired, contain, in addition to the finishing agent, other materials employed in textile finishing such as plasticizers, softening agents, hand builders, and the like.

The amount of finishing agent to be applied to the fabric varies widely depending upon the type of fabric and its intended application, and, accordingly, the present invention comprehends the use of any effective amount. Amounts of from about l to about 30 per cent by weight of the finishing agent, based on the weight of the textile fabric, are ordinarily employed, i.e., an addon of about 1 to about 30 per cent. It is preferred to employ an amount of at least about 4 per cent. In any particular finishing operation the add-on will depend upon the concentration of the finishing agent in the treating solution and the weight of solution which the textile fabric will retain, i.e., the wet pick-up. A wet pick-up of from about 50 to about 120 per cent may be readily effected by conventional techniques, while the treating solution applied to the textile fabric in practicing this invention may contain from as little as about 2 per cent, or less, to as much as about 25 per cent, or more, of the finishing agent. Accordingly, no difficulty is encountered in achieving the desired add-on.

The methylolated alkoxyalkyl carbamates of this invention, like the nitrogenous textile finishing agents of the prior art, require curing following application to the textile fabric to promote reaction with the fibers of the fabric and thereby impart the desired properties, such as wrinkle resistance and wash-wear characteristics. Suitable catalysts for the curing reaction are metal salts of strong mineral acids, particularly zinz fluoborate and the hydrates of magnesium chloride and zinc nitrate. The catalyst is ordinarly added to the aqueous treating solution and should be employed in a concentration sufficient to give a retention of catalyst of about 0.5 to about weight per cent, based on the weight of the fabric. Larger amounts of catalyst, within the range specified, are preferably employed at the higher add-on levels of the finishing agent. The optimum amount of catalyst varies depending on the particular catalyst employed. For example, with magnesium chloride it is preferred to utilize a ratio of catalyst to finishing agent by weight, as retained on the fabric, of from about 0.2 to about 0.6, while with zinc nitrate or zinc fluoborate the preferred ratio is from about 0.05 to about 0.2.

Following application of the aqueous treating solution, the fabric is subjected to heating to remove the water and then curing is effected by the application of further heat. It is preferred to dry the fabric at temperatures lower than those employed in the curing. Thus, drying is usually carried out at temperatures of up to about C., while temperatures from 150C. to about 200C. are ordinarily employed in the curing step. The time required to effect the curing will vary from as little as about 1 minute, or less, to as much as about 5 minutes, or more. Normal curing, i.e., curing immediately after drying, or deferred curing,,i.e., after the fabric has been made into a garment, may be employed as desired.

Resistance to chlorine damage caused by hypochlorite bleaching, and durability to conditions promoting acid hydrolysis, such as acid scouring, are important considerations in the art of finishing cellulosic textile fabrics. Textile fabrics treated by the method of this invention are, in many instances, possessed of superior resistance to chlorine. damage and/or enhanced durability to acid hydrolysis as compared with fabrics treated with the methylolated alkyl and hydroxyalkyl carbamates of the prior art. In particular, it has been found that the methylolated alkoxyalkyl carbamates are, in general, equivalent in resistance to chlorine damage to the methylolated alkly carbamates, but superior in durability to acid hydrolysis. On the other hand, the methylolated alkoxyalkyl carbamates have been found to be, in general, equivalent in durability to acid hydrolysis to the methylolated hydroxyalkyl carbamates, but superior in resistance to chlorine damage particularly in that they exhibit excellent resistance to chlorine damage even when the fabric treating and curing conditions are varied widely whereas the methylolated hydroxyalkly carbamates exhibit undesired criticality as regards the fabric treating and curing conditions necessary. These are important and unexpected differences which, in part, serve to distinguish the present invention from the prior art.

In addition to their excellent resistance to acid hydrolysis, and consequent durability to laundering, and their ability to provide a fabric which will not be harmed by hypochlorite bleaching, the methylolated alkoxyalkyl carbamate finishing agents described herein provide improved abrasion resistance and, in certain instances, a more desirable hand, as compared with the methylolated alkyl and hydroxyalkly carbamates. Moreover, they are more efficient on a molar basis and equally as efficient on a weight basis as the prior art finishing agents.

Evaluation of textile fabrics treated by the process of this invention was in accordance with test procedures of the Americal Society for Testing Materials (ASTM) or the American Association of Textile Chemists and Colorists (AATCC), or by procedures that are fully described herein. The following tests were conducted:

Wash-Wear Rating determined by AATCC Tentative Test Method 88A-1964T. The rating, which is indicative of the smoothness of appearance of the fabric, ranges from 1 to 5 with intermediate ratings indicated by and symbols.

Crease Recovery measured by AATCC Tentative Test Method 66-1959T.

Tensile Strength measured by ASTM Method D39-49 (Grab Test) Tear Strength measured by ASTM Method D1424-56 (Elmendorf) Abrasion Resistance measured by ASTM Method D1175-51T-B.

Damage Due to Retained Chlorine measured by AATCC Standard Method 92-1962.

Durability to Acid Hydrolysis samples of treated fabric were hydrolyzed for minutes at (SO-C. in Clark and Lubs buffer solutions at controlled pH, then washed in cold water, ironed dry, conditioned, and tested for dry crease recovery.

The invention is further illustrated by the following specific examples of its practice EXAMPLE 1 Samples of desized, scoured, bleached and'mercerized white cotton printcloth having a thread count of X 80 were padded with a treating batch containing the methylolated methoxyethyl carbamate using a Butterworth Laboratory Padder. In each instance, the treating bath was composed of methylolated methoxyethyl carbamate, MgCl2. 6H O, Fabritone PE (a commercial softner composed of emulsitied polyethylene was of 30% solids content) and TERGITOL TMN (trade-mark for a nonionic surfactant characterized as a trimethyl nonyl ether of polyethylene glycol) with the balance being water. After treatment, the wet fabric was placed on a pin tenter frame, dried at C. for 1.5 minutes, and cured at 175C. for 1.25 minutes.

For comparison purposes, identical samples of the cotton print-cloth were treated in the same manner as described above, but employing methylolated ethyl carbamate in place of the methylolated methoxyethyl carbamate. The methylolated ethyl carbamate was prepared under the same reaction conditions at a formaldehyde to ethyl carbamate mole ratio of 2.2 to 1 (the' reaction mixture consisting of 89 grams of ethyl carbamate, 66 grams of p-formaldehyde and 90 grams of water) and the treated fabric samples were dried and cured under identical conditions to those described above in connection with the methylolated methoxyethyl carbamate. The treating bath compositions and the add-on levels, which were the same in each particular run for both the methylolated methoxyethyl car- 30 bamate and the methylolated ethyl carbamate, are

summarized in Table 1 below: while the properties of the treated fabric are summarized in Table 11, fabric samples treated with methylolated ethyl carbamate being designated by the letter A and those treated with 35 methylolated methoxyethyl carbamate by the letter B.

TABLEl Treating Bath by weight) Add-On (7: on weight of fabric) Run No. Finishing Agent MgC1 .6H O Fabritone PE TERGlgOL Finishing Agent MgClg-6Hg0 Fabritone PE TABLE 11 V Tensile m p I m Abrasion 7 Dry Crease Recovery Tear Stren th Strength 1 Resistance Recovery After Fabric Warp Filling Warp Fil ing Filling Wash-Wear Rating (cycles to Hydrolysis'at Sample (degrees) (grams) (lbs) Tumble Dry Spin Dry break) pH of 2 l-A 233 1270 19 2+ 2 691 204 I-B 232 1300 21 2 2 894 214 As evidenced by the data in Tables land 11, the methylolated methoxyethyl carbamate finish of this invention, employed with fabric samples identified by the letter B, gives improved tear strength, abrasion resistance 8 prepared by reaction of equimolar quantities of ethylene carbonate and ammonium hydroxide in aqueous solution at C. to 10C. for 2 hours, in a ratio of 2 moles of p-formaldehyde per mole of hydroxyethyl carand durability to acid hydrolysis as compared with the bamate. methylolated ethyl carbamate of the prior art, em- The carbamate finishing agents were applied to samployed with fabric samples identified by the letter A, ples of desized, scoured, bleached and mercerized while giving at least equal performance with regard to white cotton printcloth having a thread count of 80 X other fabric properties. Moreover, it was found that the 80 at several levels of finish and catalyst add-on using methylolated methoxyethyl carbamate provides a 1 a Butterworth Laboratory Padder. In each case, the treated fabric with a more pleasing hand than the fabric catalyst employed was MgC1 6H O and the treating treated with methylolated ethyl carbamate. bath contained 0.1 per cent by weight TERGlTOL TMN. After treatment, the wet fabric was placed on a EXAMPLE 2 pin tenter frame, dried at 150C. for 1.5 minutes, and I5 cured at 175C. for 1.25 minutes. The add-on levels Several methylolated alkoxyalkyl carbamates were and the properties of the treated fabric are summarized prepared and evaluated as finishing agents for cotton in Table 111 below.

Table III Loss in Add-On Wash-Wear Tensile (72 on wt. of fabric) Dry Crease Tear Tensile Rating Strength Recover Strength Strength Due to Finishing Warp+Fi1lmg Warp+Filling Filling Tumble Spin Retained Finishing Agent Agent MgCl .6H O (degrees) (grams) (lbs) Dry Dry Chlorine(%) Methylolated hydroxyethyl 4 3 25 l 790 23 4 2+ N.D. carbamate 8 l 256 900 28 3+ 2+ ND. 8 2 264 860 28 4 3 ND. 8 t 3 269 680 19 4 4- 74 8 4 276 810 25 4 4 ND. 12 3 260 690 22 5- 5- ND. Meth lolated methoxyethyl 4 3 255 660 24 4 2 10.5 carhamate 8 l 237 850 24 4- 3+ ND. 8 2 266 710 24 4 3+ ND. 8 3 263 640 24 5 4 l3 8 4 273 550 23 ND. 4 ND. 12 3 267 660 21 5- 4 0 Meth lolatcd ethoxyethyl 4 3 247 610 18 4 3+ N.D. carlaamatc 8 l 252 660 24 4 3+ ND. 8 2 253 590 '21 4 3 ND. 8 3 270 570 20 ND. ND. 8 4 263 580 22 5- 4 ND. 12, 3 272 580 23 5 4 N.D. Methylolated hutoxycthyl 4 3 235 620 19 4- 2 ND. carbamate 8 l 229 720 29 3-- 2- ND. 8 2 237 660 26 4- 4- ND. 8 3 256 600 4 3 0 8 4 263 560 22 4 4 ND. 12 3 246 640 22 4 4 ND. Mcthylolatcd iso butoxyethyl 4 3 247 600 22 4 3 ND. carbamate 8 1 207 770 2- 1 ND. 8 2 I 226 640 26 3+ 2+ ND. 8 3 259 620 21 4 4- 0 8 4 258 580 26 5 4- ND. 12 3 247 640 22 4 2+ ND.

"ND. not determined.

fabrics and methylolated hydroxyethyl carbamate was As evidenced by the data in Table 111, the loss in prepared and similarly evaluatd for comparison purstrength of the fabric due to chlorine damage is very poses. The methylolated alkoxyalkyl carbamates were much less with the methylolated alkoxyalkyl carbaprepared by dissolving p-formaldehyde in an aqueous mates of this invention as compared with the methylolsolution of the corresponding alkoxyalkyl carbamate ated hydroxyethyl carbamate of the prior art. For ex- (prepared by reaction of urea with the appropriate glyample, at an add-on of 8% of finishing agent and 3% of col ether in the presence of zinc acetate catalyst) in an catalyst, the strength loss due to retained chlorine was amount of 2 moles of p-formaldehyde per mole of al- 74% with the methylolated hydroxyethyl carbamate as koxalkyl carbamate, heating to about 80C. to dissolve compared with a maximum of 13% for the four methylthe p-formaldehyde, and then permitting the mixture to olated alkoxyalkyl carbamates evaluated. Moreover,

stand at room temperature for several hours. The methylolated hydroxyethyl carbamate was prepared by reacting p-formaldehyde with hydroxyethyl carbamate,

the data indicate that the methylolated alkoxyalkyl carbamates provide, in general, at least comparable performance to the methylolated hydroxyethyl carbamate as regards crease recovery, wash-wearcharacteristics, and fabric strength.

EXAMPLE 3 tions under which the methylolation of the methoxyethyl carbamate was carried out and the properties of the fabric samples treated with the finishingagents produced under the differing conditions are sum- This example demonstrates the effect of methylolai d i Tables 1V, V and V1 for test series one, tion conditions on the performance of methylolated d three respectively.

TABLE IV Molar Ratio Dry Tensile Loss in Tensile of Reaction Reaction Crease Recovery Tear Strength Strength Strength Due to Formaldehyde Initial time Temperature Warp+Filling Warp+Filling Filling Retained Chlorine to Carbamate pH (hrs.) (C.) (degrees) (grams) (lbs) (/t.)

1:1 2 103 199 1260 28 N.D." 1.5:] 10 2 103 237 1130 23 ND. 2:1 10 2 103 257 1060 22 ND. 2.521 10 2 103 268 1010 22 9 3:1 10 2 103 274 930 22 13 "ND. not determined flwr m m v V i TABLE V Molar Ratio Dry Tensile Loss in Tensile of Reaction Reaction Crease Recovery Tear Strength Strength, 2 Strength Due to Formaldehyde Initial Time Temperature Warp-l-Fllhng Warp+Filling Filling Retained Chlorine to Carhamate pH (hrs.) (C.) (degrees) (grams) (lbs.)

1:1 10 2 103 197 1170 27 N.D." 1.5:] 10 2 103 231 1120 24 ND. 2:1 10 2 103 267 1040 23 7 :1 10 2 103 273 960 22 5 3:1 10 2 103 233 930 19 4 "ND. not determined TABLE VI Molar Ratio I Dry Crease Tear Tensile Loss in Tensile of I Reaction Reaction Recovery Strength Strength, Strength Due to l-ormaldehydc Initial Time Temperature Warp-l Filling Warp+Filling Filling Retained Chlorine to (arbamate pH (hrs.) (C.) (degrees) (grams) (lbs) ("/a) 11) 2 103 258 1090 26 12 8 2 103 254 1010 23 23 6 2 103 264 1020 24 10 4 2 103 257 1070 25 21 .....:l 10 0.25 103 265 1040 26 10 2.211 10 0.5 103 263 .1040 24 5 2.2:] 10 l 103 259 1060 27 4 2.211 10 5 103 260 1120 22 12 2.2:1 l0 2 253 1020 20 23 22:1 10 2 257 1070 28 25 methoxyethyl carbamates as a finishing agent for cellulosic textile fabrics. in the first test series, the fabric employed was a cotton printcloth having a thread count of 80 X 80, a dry crease recovery of 158, a tear strenght (warp filling) of 1,180 grams, and a tensile strength (filling) of 37 lbs; the catalyst was MgCl .6H O; the add-on was 4% of methylolaed methoxyethyl carbamate and 1.2% of catalyst; and the treated fabric was dried for 1.5 minutes at C. and cured for 1.25 minutes at 175C. In the second test series, the same cotton printcloth was employed; the catalyst was Zn(NO 6H O; the add-on was 4% of methylolated methoxyetyl carbamate and 0.2% of catalyst; and the treated fabric was dried for 1.5 minutes at 150C. and cured for 1.25 minutes at C. In the third test series, the fabric was a cotton broadcloth having a thread count of 136 X 64, a dry crease recovery of 155, a tear srength (warp filling) of 1,520 grams, and a tensile strength (filling) of 61 lbs; the catalyst was MgCl .6H O; the add-on was 4% of methylolated methoxyethyl carbamate and 1.6% of catalyst; and the treated fabric was dried for 1.5 minutes at 150C. and cured for 1.25 minutes at C. The reaction condi- As evidenced by the data Tables 1V, V and V1, the

methylolated alkoxyalkyl carbamate finishing agents of the present invention can be prepared over a relatively broad range of methylolation conditions and still perform effectively. The molar ratio of formaldehyde to alkoxyalkyl carbamate is the most significant variable, with crease recovery increasing and both tear strength and tensile strength decreasing with increasing formaldehyde to alkoxyalkyl cabamate ratios.

EXAMPLE 4 80 X 80 and in each instance it was padded with a Butterworth Laboratory Padder at a wet pick-up of 80% and then dried on a pin tenter frame at 150C. for 1.5 minutes.

Although the invention has been illustrated by the preceding examples, it is not to be construed as limited to the materials employed therein, but rather the invention encompasses the generic area as hereinbefore dis- TABLE VI] Methylolation Conditions Molar Ratio of Fabric Treatment Formaldehyde Treating Curing Curing Test Finishing to Time Temp Bath Add-On (72 on wt. of fabric) Temperature Time No. Agent Carbamate pH (Hrs) (C.) pH Finishing Agent Catalyst (F.) (mins.)

Methylolated A-l methoxyethyl 2.2 10 2 Reflux 7.0 4 1.6 350 1.25

carbamate A-2 do. 2.2 l' 2 Reflux 4.5 4 1.6 320 3.0 A-3 do. 22' l0 2 Reflux 4.5 4 l.6 350 1.25

Methylolated B-l hydroxyethyl 3.3" 2 Reflux 7.0 4 1.6 350 1.25

carbamate B-2 do. .5 l0l l 2 50 4.5 4 1.6 320 3.0 B-3 do. 2.5 lO-l l 2 50 4.5 4 1.6 350 1.25 B-4 do. 2.2 10 2 Reflux 7.0 4 1.6 350 1.25 B-5 do. 2.2" l0.5 2 50 7.0 4 1.6 350 1.25 B-o do. 2.2" 10.5 2 50 4.5 4 1.6 350 1.25 5-7 do. 2.5 [0-1 1" 2 50 7.0 4 1.6 350 l.25

"Methylolation with p-formaldehyde (95%) *Methylolation with formalin (37.57:) ""lnitial pH 'Constnnt pH throughout methylolation reaction TABLE VIII Dry Tensile Loss in Tensile C reuse Recovery Tear Strength Strength Strength Due to Test Warp+Filling Warp/Filling Filling Wash-Wear Rating Retained Chlorine No Finishing Agent (degrees) (grams) tlbs.) Tumble Dry Spin Dry (71) Methylolated A-l methoxyethyl 255 450/210 23 4 3- 2 carbamate A-2 do. 263 460/200 N.D." ND. 3 A-3 do. 260 460/170 19 4+ 3+ 6 Methylolated B- l hydroxyethyl 257 500/210 23 4+ 3 0 carbamate B-2 do. 253 460/200 23 N.D. N.D. 26

B-3 do. 260 530/220 23 ND. ND.

B-4 do. 244 500/220 23 4 3+ 60 B-ti do. 239 530/220 23 4 3+ 87 B-7 do. 243 530/260 20 ND. ND. 87

"'ND. not determined 7 As evidenced by the data in Tables VII and Vlll,;

methylolated hydroxyethyl carbamate will provide good resistance to chlorine damage only if a very high formaldehyde to carbamate ratio is employed in effecting the methylolation, with the resulting disadvantage of a very strong formaldehyde odor in the fabric. Moreover, changes in the pH of the treating bath or the curing conditions strongly influence the resistance to chlorine damage for fabric treated with methylolated hydroxyethyl carbamate, but have little effect on the resistance to chlorine damage of fabric treated with methylolated methoxyethyl carbamate. Accordingly, much less stringent control of fabric treating conditions is permissible with the methylolated methoxyethyl carbamate. This is an important distinction between the methylolated alkoxyalkyl carbamate finishing agents of this invention and the methylolated hydroxyalkyl carbamate finishing agents of the prior art.

closed. Various changes and modifications can be made in practicing the present invention without dewherein R is an alkyl group of l to 8 carbon atoms, R is an alkylene radical of 2 carbon atoms, and n is an integer having a'value of 1, said reaction being conducted at from about 20C. to about the reflux temperature of the reaction mixture for a period of time from about minutes to about 24 hours at an initial pH of from about four to about ten in a ratio of about 1.5 to about three moles of formaldehyde per mole of alkoxyalkyl carbamate.

2. The process of claim 1 wherein R is an alkyl group of l to 4 carbon atoms.

3. in a method for imparting wash-wear properties to cellulosic fabrics by treatment with a cross-linking agent followed by curing at an elevated temperature, the improvement for obtaining improved chlorine resistance which comprises employing as the cross-linking agent a product obtained by the reaction of formaldehydc in an aqueous alkaline solution with a glycol ether carbamate having the formula:

II R- (OCH-CH) -O-C-NHZ wherein R is methyl; R is hydrogen; and x is l.

@ UNITED STATES FATE QFFICE QERTIFICATE i QGEUHN Patent No. a 822 Dated March 18 9 1975 f Inventor(s) G. Goodman, Jr. et al It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Colutm 1, lines 24-25 should read: I "such as hydroxyethyl or hydrox ropyl VP carbamate, and have been observed to suffer Q from certain deficiencies, for example, with re-".

Column 6, line 9, "was" should read =-=wax--.

Column 10, line 4, the word "reaction" should appear after "differing" 7 igned and .caled this ninth Day Of September 1975 [SEAL] Arrest:

RUTH C. M ASON C. MARSHALL DANN Alrz'stmg ()jjlcer ('ummisus'imur /Parents and Trademarks Disclaimer 3,871,822.Hem y G. Goodman, J 1 "White Plains, 061ml A. Dupmz, Flushing (Corona) and Gearge H. Lomgam, New City, NY. TREATMENT OF CELLULOSIC TEXTILE FABRICS XVITH METHYLOL- ATED ALKOXYALKYL CARBAMATES. Patent dated Mar. 18, 1975. Disclaimer filed July 8, 1975, by the assignee, Um'on Uarbz'de Umpomtz'on.

Hereby enters this disclaimer to claims 1 t0 4 of said patent.

[Ofiicz'al Gazette Febwuarg 10 1.976.] 

1. A PROCESS FOR TREATING CELLULOSIC TEXTILE FABRIC COMPRISING THE STEP OF APPLYING TO SAID TEXTILE FABRIC AT ELEVATED TEMPERATURES IN THE PRESENCE OF AN ACID CATALYST AN EFFECTIVE AMOUNT OF THE PRODUCT OF THE REACTION OF FORMALDEHYDE WITH AN ALKOXYALKYL CARBAMATE OF THE GENERAL FORMULA:
 2. The process of claim 1 wherein R is an alkyl group of 1 to 4 carbon atoms.
 3. In a method for imparting wash-wear properties to cellulosic fabrics by treatment with a cross-linking agent followed by curing at an elevated temperature, the improvement for obtaining improved chlorine resistance which comprises employing as the cross-linking agent a product obtained by the reaction of formaldehyde in an aqueous alkaline solution with a glycol ether carbamate having the formula:
 4. In a method for imparting wash-wear properties to cellulosic fabrics by treatment with a cross-linking agent followed by curing at an elevated temperature, the improvement for obtaining improved chlorine resistance which comprises employing as the cross-linking agent a product obtained by the reaction of formaldehyde in an aqueous alkaline solution with a glycol ether carbamate having the formula: 